Continuous method of breaking emulsions



y 0, 1933. e. H. MEINZER CONTINUOUS METHOD OF BREAKING EMULSIONS Filed July so, 1930 s sneaks-sheet 1 GOTTHOLD H. MEINZER /N [/5 N TOR 4d. NW

May 30, 1933. mzE I 1,911,839

CONTINUOUS METHOD OF BREAKING EMULSIONS Filed July 30, 1930 3 Sheets-Sheet 2 GO-TTHOLD H. MEINZER INVEN7DR A T TORNEY May 30, 1933- G. H. MEINZER CONTINUOUS METHOD OF BREAKING EMULSIONS Filed July 30, 1930 3 Sheets-Sheet 3 FIGS GOTTHOLD H. MEINZER '10 INVENTOR C4]. AM

TTORNEY Patented May 3Q, 1933 UNITED STATES PATENT OFFICE GOTTHOLD HARRY LOS ANGELES, CALIFORNIA, ASSIGNOR TO L. IBL'AKE- SMITH, OF SAN FRANCISCO, CALIFORNIA CONTINT J'OUS METHOD OF BREAKING EMULSIONS Application filed July 30, 1930. Serial No. 471,625.

My invention pertains to the art of breaking or resolving emulsions of oil and water and is specifically directed to the treatment of petroleum emulsions, though it is by no 5 means limited to such use, nor is it impeded by the presence in the emulsion of other bodies.

1 An object ofmy invention is to cheaply and expeditiously resolve such emulsions by treating them with certain finely comminuted solids which have substantially no chemical action on the constituents of the emulsion and which, for that reason, are not consumed in the treatment, but which may be separated from its products and reused indefinitely.

A further object of my invention is to conduct such treatment in a closed cycle and in a continuous operation, retaining the solid treating agents within the cycle, continuouslyfeeding the emulsion to be broken and continuously withdrawing and parting the oil and the water which result from. the resolution of the emulsion.

An object of my invention is to minimize the cost of applying the said solids to the emulsion by passing the emulsion in flow stream through a vessel in which a suficient quantity of the solids is kept permanently in a-condition of suspension.

An object of my invention is to continuously and preferentially remove free water from a mixture of water, oil and mineral treating agents while under agitation.

An object of my invention is to prevent re-emulsification of Water and oil separated from an emulsion during the withdrawal of these liquids from theseparating or resolving stage of the process.

The emulsions herein referred to consist of mixtures of oil and water, one of these liquids being very finely subdivided and its particles suspended in a continuous mass of the other. In some cases the subdivision of the disperse phase is maintained merely by 45 the interfacial tension of the films of liquid of the continuous phase adsorbed. on the surfaces of the dispersed particles; in other cases viscous liquids, colloids or finely divided solids are present at the interfaces and form skins or films surrounding the dipersed particles. Also in many cases finely divided solids (such as clay or shale in oil field emulsions) are mechanically entrained and suspended along with the emulsion particles proper. When such emulsions are broken y the penetration of the skins and the coalescence of the dispersed liquid particles we obtain as product a mixture of the tWQ liquids together with the material of the emulsion skin and any further solid matter Which may have been present, the dispersed liquid now being in drops or masses of such size as readily to separat from the continuous phase by gravitation.

in the class of treatments to which my present invention is directed these emulsions are broken by contacting them simultaneously with two finely divided solid materials, one having a preferential surface attraction or wettability for water, the other a preferit ential attraction for oil. Numerous such materials areknown and their selection and preparation are described in detail in my copending applicaton entitled Method of resolving emulsions, filed July 30, 1930, under Serial No. $1,627. For the purpose of describing the functioning of my present invention it is sulhcient to say that ser entine, asbestos, mica, glass, calcite, barite an .quarta (or sand) are suitable water-wettable materials while magnetite, pyrite (or artificially prepared iron sulfid), gs-lena, copper, anti mony and silver are suitable oil wettable ma terials. here further reference is made to quartz and to pyrite it will be understood that the other materials mentioned are grouped with them,

For the purpose of my invention a substance belonging to each of the groups is reduced to a ratherfine state of comminution, "for example such as will an mesh screen and be retained on a screen of mesh. For reasons which will appear it is desirable that fines should be eliminated so far as possible. These substances have, so far as is known, no material chemical action on any of the constituents of the emulsion and function by drawing apart the aqueous and the oleag'inous elements and coalescing the disperse phase Eli till

into masses of such size as will readily stratif If kept clean and free from accumulations of colloidal emulsifying agents or other incidental bodies, the solids may be retained in the apparatus and will continue to function indefinitely.

With this explanation, the objects and advantages of my invention of a paratus will be evident froman inspection 0 the attached drawings and the following description thereof in which Fig. 1 is a vertical elevation of a preferred form of my apparatus, parts being broken away to show the internal construction thereof;

Fig.2 is a horizontal section through the same apparatus on the line A-B of Fig. 1;

Fig. 3 is a horizontal section through a simplified form of apparatus in which the prigiciples of the first form are embodied; an

Fig. 4 is a plan of the same modification.

Referring to the drawin s, 1 is a vaportight tank or treatin cham r havin a cov er 2 and surmounte by a dome 3. 0 this dome it is desirable to attach a pressure re lief valve 4 and a vacuum relief valve 5. The finely divided mineral used in the treatment may be inserted by removing the dome cover 6.

A feed pum 7 takes suction throu h a pipe 8 on a tan or other source of supp y of emulsion or emulsified oil not shown, and delivers this raw material into tank 1 throu h a pipe 9 which terminates at approximate y the evel indicated at 10. An automatic float valve consisting of acock or valve 11 actuated by a float 12 may be used to maintain the liquid within the tank at approximately the level indicated by the line 13.

The contents of the tank, which will be a mixture of emulsion with the solid pulverized reagents, may be kept in agitation in any desired manner, as by mechanical agitation with paddles or by circulation through pum s drawlng from and discharging into the tan I prefer however to agitate by means of circu ated compressed air or gas.

For this purpose I provide an air compressor or blower which discharges into a pipe 15 controlled by a valve 15b and thence to a branch pipe 16 controlled by a valve 165.

The latter in turn supplies a distributing manifold 17 which communicates with a series of perforated pipes 18-18, best shown in Fig.- 2, which are placed on the bottom of tls tank and through which the air or gas is' uniformly distributed over the area of the tank. The supply of gas or air is drawn from the dome 3 through a pipe 19 into a liquidtrap 20, where any condensed vapors are separated, and thence through a pipe 21 into the suction of the compressor. Condensate collecting in the trap may be "withdrawn at intervals through a pipe 22 having 'a valve 22b, and thus kept from entering the compressor. This arrangement is a safety measure onl and has no direct connection with the wor 'ng of the apparatus.

The main separating unit 23 is composed of a perforated shell 24 and a separating membrane or screen 25 supported thereby. This membrane may consist of a Woven wire screen, a slotted or punched plate screen or any of the standard filter cloths, either wire or fabric. The size of the apertures in this membrane is governed by the nature of the emulsion treated and by the size to which the mineral reagent is reduced. The apertures must be small enough to retain the reagents and lar e enough to allow any colloidal or very ne incidental solids to pass through the openings and out of the treater. The purpose of the assembly is to permit the withdrawal of the separated constituents of the emulsion while retaining the mineral reagents.

- Within the separating membrane is placed a vertical perforated drawofi pi 2 6. Between this ipe and the perforated shell 24 I prefer to orm a loosely packed layer 27 of a coarsely granular material, which may be either a preferentially water-wettable matter such as quartz or a mixture of such ma- .terial with an oil-wettable material such as pyrites. The object of this pack is to reseparate any emulsion which may, in some cases, be formed in the passage of the constituents of the emulsion through the separating membrane. It also roduces the final resolution of any traces o emulsion which may be carried forward with the separated products.

The drawofi pipe 26 delivers the resolved constituents of the emulsion into a pipe 28 through which they pass into the suction of a pump 29 and are thence delivered through a pipe 30 into an outside settling tank 31. This tank may be rovided with a swin ipe 32 communicating with a drain pipe 3 having a valve 34, for withdrawing the upper oily la er, and with a lower drawofi pipe 35 control ed by a valve 36 for withdrawing the a ueous layerand any solids which it may contain. The mixture of separated constituents discharged into this tank rapidly stratifies into the ayers described.

Around the se arating assembly 23 I place a c lindrical ba e 37, open top and bottom, an below this a bafile cone 38. The cone ma be attached to pipe 28 and the bafie attac ed to the cone by means of the posts 39 or otherwise as may be convenient, but in any case the cone does not fill the lower end of the cylinder, an annular opening 40 being left for admittin fluid into the space 41 between the bafle an the separator. The object of the baflle 37 and the cone 88 is to prevent the a 'tating gas from entering the separator an posing thence into the 13 by means of pump 7.

suction of pump 29, and further to afiord a zone of quiescence around the separator. By this means gas-locking of the pump is prevented and its continuous action ensured. As the upper end of the bafile projects above the oil level in the tank, a material amount of sedimentation of mineral takes place within the bafile and the quantity brought into contact with the membrane is correspondingly reduced, thus reducing the rate of accumulation of sediment on the membrane 25 and prolonging the period between cleanings.

The membrane being a filter will gradually choke through accumulation of solids on its outer surface. When this condition arises the two-way valve 42 is momentarily thrown into such position as to shut off communication between pipe 28 and pump 29 and to admit gas under pressure from compressor 14, through pipes 15 and 43. This gas passing into the interior of the separator causes the cake'of sediment to slough off and drop to the bottom of the tank.

For the purpose of draining the treatin tank of fluid and to permit it to be kept in operation while the membrane is being cleaned as above, I provide the auxiliary separator 44 located just above the distributing pipes 18 and near the bottom of the tank. This separator is provided with a erforated screen 45 surrounded by a mem rane 46. the outer end of thisassembly being closed asat 47 and the inner end communicating through a pipe 48, with pipe 28 and thus with the suction of pump 29. This separator may also desirably be provided with a gas inlet connection from pipe 43- and a two-way cock 49 by means of which the membrane 46 may be cleaned. By the use of this dual connection the continued operation of the apparatus is made possible.

The apparatus of Figs. 1 and 2 functions in the following manner. A sufiicient charge of the solid reagent is placed in tank 1 which is then filled with emulsified oil to the level Compressor 14 is then started and the contents of the tank are thus agitated until thoroughly mixed and the agitation continued until the emulsion is broken. At this stage the tank contains free oil suspending coarse also all the reagents.

- Pump 29 is then started and pump 7 contin ues to deliver into the tank a sufficient quantity of emulsified oil to replace the fluid withdrawn. rated fluids in the tank and is itself continuously resolved. The intermixed but demulsified fluids gradually pass into the quiet zone 41 in which a material proportion of the relatively heavy solids settle outand pass to the bottom of the tank, where they are caught up and again suspended. The fluids and such colloidal or very fine solid matter as they globules of water and This emulsion mixes with the sepa may carry pass through the filteringmembrane and thence to settling tank 31.

' The filter being much more permeable to water than to oil, because of the lower viscosity, tends constantly to withdraw water preferentially from the mixture and thus free water is withdrawn as fast as it is set free and its proportion in the mixture held at a desirableminimum. The reacting solids accumulatingi on the membrane are cleaned off from time to time and are thus retained in the pinion 56 which in turn is carried on a shaft 57 and revolved by means of a pulley 58 from any convenient source of power not shown.

To the lower end of the shaft and just clear of the bottom of the tank I afiix a scraper or paddle 59 for keeping the contents of the tank in agitation and to the sides of the tank, at convenient points,'a number of baflles 60-60 to prevent the contents of the tank from revolving.

On one side of the tank, or elsewhere within it as may be preferred, I form a pocket or chamber 61 of which one side is left open. Over this open side I fasten, in any convenient manner, a fine screen or filter 62, which should be flat and preferably fixed in a substantially vertical position. This filter may be made of woven wire screen or slotted or unched plate screen or even of filter cloth; it should be as coarse as the mesh of the treat ing agents will permit and should be so supported, as by an underlying perforated plate, as to maintain a flat surface. A scraper 63 attached to a hand rod 64 is positioned in contact with the fiat filtering surface by means of a bracket 65 and a sleeve 66. By a vertical movement of this scraper any accumulation of sediment on the filter may be removed.

The treating tank 50 is supplied with the emulsion to be treated by means of a pipe 67 controlled by a valve 68 and communicating with any source of supply not shown. The discharge from this pipe may pass directly into the tank or it may enter a funnel 69 affixed to the upper end of a pipe 70 which enters'the tank at its lowerend. It is desirable to introduce the emulsion feed at or near the bottom of the tank.

A separating tank 71 which may be of enerally similar dimensions to those of tan 50 is placed closely adjacent the latter. It is desirable that the tops of these two tanks shouldbe substantially at the same level and 1 The separated cated at 75, conducts separated water into a launder 76 b which it may be conducted to any drain. y makin the overflow level of 7 4 slightly lower t an that of pi e 7 2 the rence in weight between the co umn of water inthe former and'the combined water and oil column in the tank may be offset and, if the size of the tank is suflicient to permit complete separation, contmuouslydischarge each its appropriate liquid without attention.

A pipe 77 is arranged to communicate between the interior of the chamber 61 and the interior of tank 71. This pipe should be of relatively large diameter and as it is submerged at all timesthe mixture of separated liquids will be conducted through it with a minimum of turbulence.

The 0 ration of this apparatus is as follows. mulsion entering through pipe is intermixed with the contents of tank 50 which are automatically maintained at the level 78 fixed by the overflow pipe 7 2. The suspended solid reagents cause the resolution of this emulsion as fast as it enters. The Eroducts of this resolution pass throu h the lter 62 carrying any fine foreign so id or colloidal matter and leavin the coarse reagent materilal behind. is reagent remains permanently in the treatin tank and will treat an indefinite amount 0? emulsion. constituents flow gently into the separatin tank, the oil rises to the surface and over ows through pipe 72, the water settles and overflows through pipe 74, and

' any mud which may collect at the bottom of the separating tank may be withdrawn from tsine to time by opening valve'79 in drain pipe The chamber 61 may desirably be filled with a loose pack of the treating solids, as described above, and any other or preferred means for cleaning its surface may be substituted for the simplescraper shown.

It is entirely possible to break the emulsion by simple agitation with the described materials in an open tank, to settle or filter the minerals from the separated fluids with any preferred type of filter and to return the minerals to the, tank to treat another batch of emulsion. By making the withdrawal, feed, filtration and return of minerals continuous such an apparatus might be made to function continuously. The advantages of the apparatus here described are: First, that the system being closed and the same air or the two overflows willgas being continuousl not eva rated'or oxi ized by the gas or air whichis passed through it for agitation; second that a zone of ciuiescence being formed about the filtering e ement the quantity of solid to be filtered-from the se arated liquids is greatly reduced; third, t at the filter being placed within the treating tank no abrasive material has tobe handled throu h a ump and the solid matter is retaine in t e tankat all times and does not have to be returned thereto. In a process such as this, where there is no cost for treating material (once a suflicient supply is introduced) and where commercial requirements are such that the treatment must be conducted with the most extreme economy of labor and power in order to be competitive, these advantages are highly material and important.

I claim as my invention:

1. A-method of breaking an oil and water emulsion, comprising: establishing a body of said emulsion; simultaneously suspending in said body1 a plurality of dissimilar soli substances avin'g jointly the property of resolving said emulsion into its oil and water constituents at a desired and substantial rate; continuously agitating said body to maintain said suspension and to promote said resolution; continuousl adding emulsion to said body; continuous y with rawing said resolved constituents from said body while retaining said 'solid substances within said body, and partin said constituents.

2. A method 0 breaking an oil and water emulsion, comprising; establishing a body of said emulsion; simultaneously suspending in said body a plurality of dissimilar comminuted solid substances having jointly the property of resolving said emu sion into its oil and water constituents ata desired and substantial rate; continuously agitating said body by passing streams of gas t erethrough to maintain said suspension and to promote said resolution; continuously addin emulsion to said body; continuously with rawing said resolved constituents from said body while retaining said solid substances within said body, and parting said constituents.

3. A method of breakin an oil and water emulsion, comprising: esta lishing a body of said emulsion; suspending in said body comminuted solid substances having the property of resolving said emulsion into its oil and water constituents; agitating said body by passing streams of gas therethrough to maintain said suspension and to promote said resolution; collecting said gas from above said body and returning it to roduce further agitation; continuously addlng emulsion to said body; continuously withdrawing said resolved constituents from said body while retaining said solid substances within said body, and parting said constituents.

circulated, the oil is 4. A method of breakin an oil and water emulsion, comprising: esta lishing a body of said emulsion; suspending in said body comminuted solid substances having the property of resolving said emulsion into its oil and water constituents; agitating said body to maintain said suspension and to promote said resolution; maintaining a zone of quiescence within and substantiall separated from said body; continuously ad ing emulsion to said body; continuously withdrawing said resolved constituents from said zone while retaining said solid substances within said body, and partin said constituents.

5. A method 0 breakin an oil and water emulsion, comprising: esta lishiug a body of said emulsion; suspending in said body comminuted solid substances h ving the property of resolving said emulsionlnto its oil and water constituents; agitating said body by passing streams of gas therethrough to maintain said suspension and to promote said resolution maintaining a zone of quiescence and of gas exclusion withinsaid body; continuously addingemulsion to said body; continuously withdrawing said resolved constituents from said zone while retaining said solid sub stances within said body, and parting said constituents.

6! A method of breaking an oil and water emulsion, comprising: establishing a body of said emulsion; suspending in said body comminuted solid substances having the property of resolving said emulsion into its oil and water constituents; agitatirg said body by passing streams of gas there rough to main tain said suspension and to promote said resolution; collecting said gasfroin above said tinuous body and returning it to produce further agitation; maintainmg azone of quiescence and of as exclusion within said body; conadding emulsion to said body; continuously withdrawing said resolved constituents from said zone while retaining said solid substances within said body, and partin said constituents.

A method of breakin emulsion, comprising: esta lishing a body of said emulsion; simultaneously suspending in said body a plurality of dissimilar comminuted solid substances having jointly the property of resolving said emulsion into its oil and water constituents at a desired and substantial rate; continuously agitating said body to maintain said suspension and to promote said resolution; continuously adding.

emulsion to said body; continuously withdrawing said resolved constituents from a substantially separated zone within said body while retaining said solid substances within said body; continuously resolving any emul- "sion withdrawn with said constituents by passing said constituents throu' h a retained body of said solids maintaine 'withm said anoil and water emulsion body, and parting said constituents.

8. A method of breaking an oil and water emulsion, comprising: establishing a body of sai d emulsion simultaneously suspending in said body a plurality of dissimilarsolid substances having jointly the property of resolving said emulsion into its oil and water constituents at a desired and substantial rate continuously agitating said body by passing streams of gas therethrough to maintain said suspension and to promote said resolution; continuously withdrawing said resolved constituents from said body while retaining said solid substances within said body; continuously resolving any emulsion withdrawn with said constituents by passing said constituents through a retained body of said solids maintained within said emulsion body, and parting said constituents.

9. A method of breakin an oil and water emulsion, comprising: esta lishing a body of said emulsion; susp nding in said body comminuted solid substances having the property of resolving said emulsion into its oil and water constituents; agitating said body by passing streams of gas therethrough to maintain said suspension and to promote said reso- ,-lution; collecting said gas from above said body and returning it to produce further agiresolution; maintaining a zone of uiescence within and substantially separated rom said body; continuousl addin emulsion to said body; continuous y with rawing said resolved constituents from said zone while retaining said solid substances within said body; continuously resolving any emulsion withdrawn with said constituents, and parting said constituents.

11. A method of breaking an oil and water emulsion, comprising: establishing a body of said emulsion; suspending in said body comminuted solid substances having the pro erty of resolving said emulsion into its oi and water constituents; agitating said body by passing streams of gas thereturough to maintain said suspension and to promote said resolution; maintaining a zone of quiescence and of gas exclusion within said body; continuously adding emulsion to said body; continuously withdrawing said resolved constituents from said zone while retaining said solid substances within said body; continuously resolvin any emulsion withdrawn with said constituents, and parting said contain said suspension and to promote said resolution; collecting said gas from above said body andreturning it to producefurther agitation; maintaining a zone of quiescence and of gas exclusion within said body; continuously adding emulsion to-said body; continuously withdrawing said resolved constituents from said zone while retaining said solid substances within'said body; continuously resolving any emulsion withdrawn with said constituents, and parting said constituents.

13. A method of breakin an oil and water emulsion, comprising: esta lishing a body of said emulsion; simu taneously suspending in said body a plurality of dissimilar comminuted solid substances having jointly the property of resolving said emulsion into its oil and Water constituents at a desired and substantial rate, one of said substances being preferentially wetted by oil and the other of said substances being preferentially wetted by water; continuous agitating said body to maintain said suspension and to promote said resolution; continuously adding emulsion to said body; continuously withdrawing said resolved constituents from said body while retaining said solid substances within said water; continuously agitating said body by passing streams of gas therethrough to maintain said suspension and to promote said resolution; continuously adding emulsion to said body; continuously withdrawing said resolved constituents from said body while rebeing preferentially wetted by oil and the other of said substances being preferentially wetted by wateragitating said body by passing streams of gas therethrough to maintain said sus ension and to promote said resolution; co lectin said gas from above said body and returning it to produce further agitation; continuously adding emulsion to said body; continuously withdrawing said resolved constituents from said body while retaining said solid substances within said body, and parting said constituents.

16. A method of breaking an oil and water emulsion comprising: establishing a body of said emu sion; simultaneously suspending in said body a plurality of dissimilar comminuted solid substances having jointly the property of resolving said emulsion into its oil and water constituents at a desired and substantial rate, one of said substances being preferentially wetted by oil and the other of said substances being preferentially wetted by water; continuously agitating said body to maintain said suspension and to promote said resolution; maintaining a zone of uiescence within said body; continuously adding emulsion to said body; continuously withdrawing said resolved constituents from said zone while retaining said solid substances within said body, and parting said constituents;

In witness that I claim the foregoin I have hereunto subscribed my name this 2n day of July, 1930.

GOTTHOLD HARRY MEINZER.

taining said solid substances within said body, and parting said constituents.

15. A method of breaking an oil and water I emulsion, comprising: establishing a body of said emulsion; suspending in said body comminuted'solid substances having the property of resolving said emulsion into its oil and water constituents, one of said substances 

